Journal of Petroleum Technology and Alternative Fuels Vol. 2(8), pp. 132-140, August 2011
Available online at http://www.academicjournals.org/JPTAF
©2011 Academic Journals
Full Length Research Paper
Heavy oil spill cleanup using law grade raw cotton
fibers: Trial for practical application
Hussein, M.1, Amer, A. A.2* and Sawsan, I. I.3
1
Chemical Department, Faculty of Engineering Alexandria, Alexandria University, Alexandria Egypt.
2
Alexandria Petroleum Company, Alexandria, Egypt.
3
Arab Academy for Science and Technology and Maritime Transport (AASTMT), Alexandria, Egypt.
Accepted June 6, 2011
Crude oil released to the marine environment through accidental spillage or drainage from land causes
serious damage to the environment and marine life. Treatment of oil spills remains a challenge to
environmental scientists and technologists. Sorption is a popular technique applied for treatment of oil
spillage. In this paper, the potential of raw law value cotton fibers, to remove used oil was investigated
also an attempt was made to provide an efficient, easily deployable method of cleaning up oil spills and
recovering of the oil. It is important to provide a safe system for oil removal and recovery. The results
presented and discussed in this work pointed out that the loose low grade cotton fibers and the pad
have an excellent commercial potential as a sorbent for oil.
Key words: Used oil, sorption capacity, sorbent, low grade cotton fibers pad.
INTRODUCTION
Lubricating oil is the most valuable component in a barrel
of crude oil. When it is spent (drained from the engine), it
contains a variety of contaminants which are environmentally hazardous. The world environment conference
held in Kyoto in 1997, confirmed the drastic need to
reduce petroleum waste discharge into the environment.
In fact, it was estimated that less than 45% of available
waste oil was being collected world-wide in 1995. The
remaining 55% was either misused or discarded by the
end user in the environment. Without access to suitable
treatment, used oil tends to be disposed of ways that can
degrade the environment. Used oil can be illegally
dumped into waterways or dumped on land or in landfills,
where ground water contamination can result. On the
other hand, if used lube oil is recycled properly it can
help to preserve our valuable resources as well as to
reduce its environmental impacts (Leask, 1998).
Whenever oil is spilled, there would be a potential to
cause significant environmental impact (Bucas and
Saliot, 2002). Crude oil spilt in the marine environment
*Corresponding author. E-mail: shaier2003@yahoo.com. Tel:
0020122493520. Fax: 002034401605.
undergoes a wide variety of weathering processes, which
include evaporation, dissolution, dispersion, photo-chemical oxidation, microbial degradation, adsorption onto
suspended materials, agglomeration, etc. (Jordan and
Payne, 1980). These physico-chemical changes enhance
oil dissolution in seawater (Payne and Phillips, 1985).
The methods commonly used to remove oil involve oil
booms, dispersants, skimmers, sorbents etc. The main
limitations of some of these techniques are their high cost
and inefficient trace level adsorption (Wardley-Smith,
1983). Also most of the dispersants are often
inflammable and cause health hazards to the operators
and potential damage to fowl, fish and marine mammals.
They can also lead to fouling of shorelines and
contamination of drinking water sources (NRC, 1989).
Removal of oil by sorption has been observed to be
one of the most effective techniques for complete
removal of spilled oil under ambient conditions. Various
sorbents such as exfoliated micas, chalk powder,
ekoperl, straw, sawdust, foams of polyurethane or
polyether, fibers of nylon, polyethylene etc. have been
studied for this purpose (Wardley-Smith, 1983). Since
most oil products are biodegradable, oil could be
disposed of for example by composting. A biodegradable
material with excellent absorption properties would be
Hussein et al.
133
Figure 1. SEM image of raw cotton fibers.
advantageous in this respect (Suni et al., 2004).
The purpose of this work is to study the oil sorption, in
aqueous medium by low quality grade cotton and not only
to provide an environmentally acceptable method of
cleaning up oil spills, but also to get an applicable
technique which allows its recovery.
MATERIALS AND METHODS
Raw law value cotton fibers used in the study as sorbent fibers
were sourced in Kafr Eldwar cotton gin, Egypt. The cotton fibers
were collected in the 2006 season from the different growing
regions. One type of low value cotton gin fibers (lint) by-product
from the classing process was used Afriba in this study used as
loose fibers and was packed in a polypropylene bag with the
following specifications (Nonwoven polypropylene permeable to oil
but retains the sorbent with average thickness of 65 mm, shear
modulus of 6.25 N/cm2 and modulus of elasticity (elongation of
32.2%).
Characterization of cotton samples was not carried out since the
by-product cotton bales were made up of samples from different
growing regions (that is, heterogeneous sample). Therefore, the
cotton samples used had a variety of cotton length, uniformity,
strength and colour. In addition, no cotton fibers ‘conditioning’ was
undertaken in the experimental work. The cotton fibers were
essentially used in the raw state.
Scanning electronic microscope model (SEM JEOL JSM 6360
LA" made by JEOL, Japan), was used to study the fiber surface
morphology. Before examination, fiber samples were sputter coated
with a thin layer of gold in a vacuum chamber (Valcineide et al.,
2005). Figure 1 presented SEM micrograph of surface
morphologies.
Infrared spectra were recorded on a FTIR spectrometer (JASCO
FTIR-420). UV absorbance was recorded using a GBC UV. Visible
spectrophotometer (GBC Cintra 5, Australia) with a 1 cm cell. The
viscosity of the crude oil sample was determined by a rotary
viscometer (HAAKEVT-500, Germany).The average particle size
was measured with COULTER LS 230 particle size analyzer
(Shashwat et al., 2006). The used oil was lubricating oil of the
following specification:
Determination of dynamic oil retention and oil sorption
capacity
A 500 mL sample of artificial sea water (3.5% NaCl) was placed in a
1 L glass beaker, as described in Technical Manual of the American
association of textile chemists and colorists [AATCC] (Choi and
Cloud, 1992). A forty mL of oil was added to the beaker. The
beaker containing crude oil and artificial sea water was mounted in
a shaking apparatus. The cotton (1 g) , flat cake-shaped (52 mm
diameter) obtained by squeezing, was put in the system, which was
shaking for 15 min at 105 cycles/ min The wet flat cake was
weighed after being drained for 5 min in the sustainer. Water
content of the sorbent was analyzed by the ASTM D4007-81
(ASTM, 1998a). Petroleum ether was used as the carrier solvent.
The use of a flat cake shape avoids major problems of sorbent
density variations (but it continues varying slightly) (Deschamps, et
al., 2003) (Table 1).
Oil sorption capacity = [ST-SC-SA] / SA
Where, SA is the dry weight of the sorbent (g), ST is the total weight
(g) of the oil, water and dry sorbent and SC is the weight of water
(g). All tests were triplicate and the average the three runs were
taken for calculation. If the value of any run deviates by more than
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J. Pet. Technol. Altern. Fuels
Table 1. Physical properties of used lube oil.
Specific gravity at 15°C
Kinematic viscosity cSt at 40 °C (ASTM D 1298)
Kinematic viscosity cSt at 100 °C (ASTM D 445)
Water content (ASTM D 95)
Asphaltene content wt % (IP 143)
15% from the mean of three runs, then the samples were rejected
and the test was repeated with three new specimens.
Evaluation of cyclic sorption/desorption characteristics
This experiment evaluated reusability of the low grade cotton fibers
for cyclic oil sorption/desorption. The experiments were carried out
under simulated field conditions, as described previously. The
procedure was similar to that adopted by Inagaki (Inagaki et al.,
2002). The oil recovery process was performed by squeezing out
the absorbed oils from the test cells through a piston to determine
the extent of oil sorbed by a simple mechanical device. The
squeezed sorbent was used again in the sorption process. The
weights of test cells and the oil squeezed out were measured in
each cycle. The sorption/desorption cycle was repeated for the
desired number of cycles until oil sorption capacity was less than
50% of the sorbed oil in the first cycle.
Static water test
This procedure was designed to test for water pickup under
stagnant condition (hydrophobic characteristic). The test was
performed at room temperature (22 to 25°C).
The test cell (one liter glass beaker) was filled with a layer of 80
mm water of salt water containing 3.5% by weight NaCl. One gram
of the sorbent sample was placed in a net which is lowered into the
test cell.
A lid was placed on the cell to prevent evaporation and to protect
the cell. After 15 min, the sorbent with the net was removed from
the beaker and let to drain over the beaker for 5 min. The net was
placed over a clean empty weighted watch glass to catch any
additional drips and immediately the saturated oil sorbent was
transferred to the watch glass and the weight was recorded
(Cooper and Keller, 1992).
RESULTS AND DISCUSSION
Characterization
Electro scanning of law grade raw cotton fibers
(ESEM)
Electro scanning electron microscopy has been widely
used to characterize materials, particularly their
morphological properties. The main focus is the role of
fiber morphology on the uptake of the hydrocarbons.
Cotton adsorption mechanisms: About 1 kg of low
grade cotton waste samples were fractionated into eight
fractions consisting of clean lint, hulls, sticks and stems,
grass, seeds, small leaf and trash (Shepherd, 1972).
0.9057
129.7
14.5
2.1
1.12
About 100 g of each sample was fractionated according
to the ANSI/ ASTM D 2812-95 Using Shirly analyzer
(ASTM, 2006). It was found that Afriba contained 10 %
impurities and 90 % fiber.
In general in raw cotton fiber, the principal component
is cellulose, comprising 90 to 95% of the dry fiber weight.
The remaining components are impurities such as,
proteinaceous material, 0.3 to 1% waxes, 07 to 1.2%
pectins and small amounts of organic acids and as
producing inorganic materials (Segal, 1985). Cotton wax
is an important substance that may facilitate non-polar
interaction with organic compounds such as hydrocarbons.
From the SEM image in (Figure 1), an assessment of
the fiber morphology can be obtained. Cotton fibers have
the characteristic shape of a convoluted tube which
resembles a twisted ribbon, approximately 11
in
diameter.
FTIR spectra
The FTIR spectrum (Figure 2) of cotton fibers shows
– 1
strong bands at 3352 cm
due to -OH stretching. The
- 1
band at 2904 cm
corresponds to C-H asymmetric
stretching of - CH2 - groups. The band at 1645 cm - 1 is
attributed to H - O- H bending and the bands at 2372 cm-1
are attributed to -OH stretching (Nakanishi and Solomon,
1977).
Effect of sorption time
The results of the experiments are presented in Figure 3.
Figure 3 shows that the sorption capacity increases with
increasing the sorption time until it reaches a maximum of
22.5 g oil/ g of fiber for used oil using cotton fibers and of
18.43 g oil/ g of fibers for used oil using cotton fibers
contained in the pad at sorption time of 15 min, then
these values decrease until they reach nearly constant
value of sorption capacity irrespective to the soaking time
due to the higher surface area of the loose fibers
compared to the pad containing the low grade cotton
fibers. This test was designed to study the effect of
sorption time and to simulate the field conditions where a
sorbent is used.
Hussein et al.
135
Figure 2. FITR spectra of raw cotton fibers.
Sorption time (min)
Figure 3. Effect of sorption time on the oil/water sorption capacity.
Weight of sorbent
Effect of oil film thickness
Figure 4 shows that as the weight of the fibers increases
the sorption capacity increases till it reaches a maximum
value of 22.5 g oil/ g of fiber for used oil using cotton
fibers and of 18.43 g oil/ g of fiber for used oil using
cotton fibers contained in the pad at 1 g of cotton fibers
due to big sorbent surface contacted the oil.
Figure 5 shows that the sorption capacity increases with
the oil film thickness until it reaches a maximum of 22.5 g
oil/ g of fiber for used oil using cotton fibers and of 18.43
g oil/ g of fiber for used oil using cotton fibers contained in
the pad at oil film thickness of 5 mm and that the water
pick-up decreases by increasing the oil film thickness
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J. Pet. Technol. Altern. Fuels
Weight of sorbent (g)
Figure 4. Effect of sorbent weight on the oil/water sorption capacity.
Figure 5. Effect of oil film thickness on the oil/water sorption capacity.
until it reaches the lowest value also at oil film thickness
of 5 mm.
The result indicates that the sorption capacity of cotton
fibers is enhanced by increase the oil film thickness till it
reaches the maximum value at oil film thickness of 5 mm,
the water pickup are decrease to a small value. It was
shown that as the oil increases the oil contacting surface
increases and the water contacting surface decreases.
Hussein et al.
137
Holded oil (g/g sorbent)
holded used oil in cotton fiber
Dripping time (min)
Figure 6. Effect of dripping time on the oil/water sorption capacity.
These results are in agreement with Lim and Huang
(2006) and Reed et al. (1999) as they discussed that slick
thickness and area are key variables in oil weathering
and transport models.
Dynamic oil retention
As shown in Figure 6 in general, it shows that the
dripping of oil from the surface of the cotton fibers is fast
during the first 5 min. The draining process could be due
to two reasons: First, it was the instantaneous dripping of
oil out from external surfaces of the cotton fibers
assemblies and surface of the test cells. Second, it was
due to oil draining out from the extra-lumen liquids, which
would continue over a longer period albeit slowly. The
draining of the extra-lumen liquids occurred because the
capillary pressure was insufficient to hold the weight of
the oils retained in the cotton fibers. These results are in
agreement with those reported by Choi et al. (1993), Wei
et al. (2003) and Lim and Huang (2006) where oil
retention capacity of the cotton fibers is an important
parameter in evaluating the ability of sorbents to retain
the absorbed oil during transfer and handling operations.
Effect of sorption temperature
The results of the experiments are presented in Figure 7.
Figure 7 shows that the oil sorption capacity by cotton
fibers increases with increasing the temperature until it
reaches the maximum value of 22.5 g oil/ g of fiber for
used oil using cotton fibers and of 18.43 g oil/ g of fiber
for used oil using cotton fibers contained in the pad at
25˚C then the sorption capacity decreases again. The
sorption capacity of the oil is inversely proportional to the
oil viscosity and directly proportional to the capillary
radius. It is also expected that a decrease in the
temperature would result in a decrease in segmental
mobility of the fibers, which would reduce the absorption
capacity (Choi and Cloud, 1992). A compromise between
these factors would occur.
These results agrees with the results obtained by Choi
and Kwon (1993), whose researches were on nonwovens
cotton, Johanson et al. (1973) whose reports were on
unstructured fibers and Toyoda et al. (2000) whose
studies were on exfoliated graphite.
Effect of reusability
The results of the experiments are presented in Figure 8.
The figure illustrates that oil sorption capacity decreases
during repeated use. The recovery of oil was found to
decrease and the results suggest that cotton fibers can
be reused for 3 and 5 times for the pad for oil spill
cleanup with the aid of a suitable mechanical device
which indicates that the pad enhanced the reusability.
These results are in agreement Choi and Kwon (1993)
and Deschamps et al. (2003). The sorbent is considered
reusable if a loaded sorbent can easily compress or
squeezed to its original size and shape even if there was
a tendency toward decrease in sorbent efficiency with
repeated sorption and desorption (Elsunni and Collier,
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J. Pet. Technol. Altern. Fuels
Figure 7. Effect of sorption temperature on the oil/water sorption capacity.
Figure 8. Effect of reusability on the oil/water sorption capacity.
1996). Although many efficient ways to recover oil from
the sorbent are available, compression of the sorbent is
an economical and practical method.
shows that the different kind of cotton forms have higher
sorption capacity of 22.5 and 18.43 g/ g fiber while the
commercial sorbent which has a maximum values for
used oil of 7.5 g/ g fiber.
Comparison between the different kind of cotton
wastes and commercial sorbent
Conclusions
Figure 9 shows comparison between the different kind of
cotton wastes and commercial sorbent. The results
In this study, an attempt was made to characterize and
provide insight into the adsorption phenomena of the
Hussein et al.
Used oil
139
Sorbed water with used oil
Oil sorption capacity (g/ g fiber)
25
20
15
10
5
0
Loose cotton fiber
Pad form
Sorbent type
Adsorb-it filtration fabric gray
sheet
Figure 9. Comparison between the different kind of cotton wastes and commercial sorbent.
selected sorbent material using key analytical techniques.
SEM was used to provide an insight into the adsorption
mechanism of the cotton fiber.
The experiments carried out involved low grade cotton
fibers, where their sorption capacity (g oil/ g fiber) and
water pickup were compared with a pad containing low
grade cotton fibers and taken as a measure to determine
the potential of using low grade cotton fibers in oil-spill
treatment in sea water.
The low grade cotton fibers oil sorption capacity was
found to depend on sorption time and the system
conditions such as oil film thickness and temperature and
it was found that loose fibers has a higher sorption
capacity compared to the pad containing the low grade
cotton fibers due to the higher surface area of the loose
fibers.
The majority of the sorbed oil was removed from the
natural sorbent by a simple mechanical press suggesting
that the sorbent can be used repeatedly three times in oil
spill cleanup and five times for the pad.
The holding capacity of the loose fibers and the pad
was found out to be good which means that the pad and
loose fibers can be left without dripping the sorbed oil.
The comparison between the raw low grade cotton
fibers in two forms showed that the low grade cotton
fibers in loose form have the highest sorption capacity.
Based on the total results obtained, the pad and loose
cotton fibers have an excellent commercial potential as a
sorbent for oil.
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